Progress 01/28/14 to 09/30/18

Outputs
Target Audience:Academic and industrial professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has supported a PhD student. The project has provided professional growth in management of research problems, professional writing, and supervision of students. The project provided experience in professional meeting presentations for two Ph.D. students. The project has engaged two other PhD students (one African citizen, one Iranian) all supported on other funds. Aseel M. Bala was granted a Ph.D. degree. How have the results been disseminated to communities of interest?A Ph.D. thesis has been completed. We presented three oral presentations and three poster presentations. One submitted publication is in revision, three drafts are undergoing polishing. What do you plan to do during the next reporting period to accomplish the goals?For the new S-1075 project which begins on October 1, 2018 (and replaces the S-1041 project): Thermodynamic Modeling: We will refine the model documentation and perform fitting for cross associating and multifunctional molecules in order of increasing complexity. The remaining work is with regard to fitting to demonstrate capabilities. Spectroscopy: We will finish measurements on alcohol + hydrocarbons. We also will perform measurements on selected cross associating and multifunction molecule systems. Spectroscopic interpretation: We have discovered that the methods in the literature are insufficient to deconvolute IR spectra when overlap begins to occur above 2 mol% of alcohol in hydrocarbons. For reliable interpretation, we need to deconvolute up to 10 mol%, and thus we need to develop more reliable methods using MD + QM methods to guide the fitting. Also, we plan to use fitting in the Fourier domain instead of the wavelength domain to more precisely determine the wavenumber locations of the underlying contributions. Further, we intend to explore the correlations between the NMR and IR results over the concentration range up to 10 mol% alcohol. MD + QM: We are currently running calculations with a secondary alcohol (isopropyl alcohol) to see if the same QM curve developed for primary alcohols will be followed by secondary alcohols. We will perform calculations for selected cross associating and multifunctional molecule systems.

Impacts
What was accomplished under these goals? Impact The WAG-NRTL model developed in this project is the most successful method for correlating phase equilibria data away from vapor-liquid critical points compared to other state-of-the-art models. This is the first time that the entire -OH region in the infrared spectrum can be related quantitatively to apparent concentration at moderate concentrations, independent of temperature. A poster presentation was awarded 2nd place at the CHEMS Research Forum, East Lansing, Michigan, May 10, 2018. An oral presentation was awarded 2nd place at the regional Midwest Thermodynamics and Statistical Mechanics Conference Pittsburgh, Pennsylvania, June 12, 2018. Major Activities Thermodynamic Modeling: The thermodynamic model was refined in response to industrial partner input and to fix bugs. The code has been improved to provide more debugging output and provide reporting of the individual contributions to the activity coefficients (residual, combinatorial, combinatorial correction, Wertheim). The documentation was developed and has subsequently been refined to provide examples of regression to experimental data. The code has been modified to include excess enthalpy. We have developed a method to regress association parameters in addition to the residual contribution parameters. We have termed the new method 'WAG' for Wertheim Association Gamma, and the method can be combined with traditional models. The most successful variation we call WAG-NRTL. We selected phase equilibrium data for eight binary systems containing alcohol + hydrocarbons (class 1) and alcohol + water (class 4). Both CPA and PC-SAFT utilize the same association term, but are unable to fit the systems as successfully. Spectroscopy: IR experiments are underway. In combination with the MD + QM work described below, we developed a procedure to quantify the entire alcohol -OH IR absorbance region as a function of binary composition. We have acquired a full set of NMR chemical shift data for butanol + cyclohexane at temperatures from room temperature to 60 °C. MD + QM: This topic has been renamed to avoid confusion with the use of QM/MM where the simulations are run simultaneously. For the binary system butanol + cyclohexane, to collect sufficient statistics, we performed quantum calculations on 1576 clusters containing 2376 covalent hydroxyl groups forming 800 hydrogen bonds. For ethanol + cyclohexane, quantum calculations were performed on 1731 clusters containing 3285 covalent hydroxyl groups and 1554 hydrogen bonds. We developed a procedure which entails scanning the molecular dynamics Amber trajectory to identify and categorize clusters, selecting and saving cluster coordinates, passing them to Gaussian to perform a low level minimization, performing a high level minimization and frequency analysis, using MATLAB to recheck the output to reclassify the bonding type if it is changed, and finally interrogating the results for patterns and results. Spectroscopy Analysis: We used the MD + QM results to develop a curve for the infrared extinction coefficient vs. wavenumber for butanol + cyclohexane and ethanol + cyclohexane. The curves were found to overlap and were fitted with a universal curve. The curve provides a universal scaling of the total hydroxyl content in solutions. Previously, the entire -OH region in the IR spectrum could not be quantitatively related to the overall species concentration except at very dilute concentrations because the region is broad and changes shape significantly with temperature. We are now able to quantify at all temperatures and compositions. NMR data have also been obtained and fitted over the temperature range for butanol + cyclohexane.

Publications

• Type: Theses/Dissertations Status: Published Year Published: 2018 Citation: Bala Ahmed, Aseel M.A.; Fundamental Studies and Engineering Modeling of Hydrogen Bonding, Ph.D. Thesis, Michigan State University, August 2018.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Killian, W.G.; Bala, A.M.; Peereboom, L.; Kakeshpour, T.; Jackson, J.E.; Lira, C.T. Quantum-Guided Spectroscopy of Alcohol/Hydrocarbon Liquid Binary Solutions to Quantify Hydrogen Bonding, Oral presentation at the University of Pittsburgh, Midwest Thermodynamics and Statistical Mechanics Conference Pittsburgh, Pennsylvania, June 12, 2018. 2nd Place Award.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Killian, W.G.; Bala, A.M.; Peereboom, L.; Kakeshpour, T.; Jackson, J.E.; Lira, C.T. Quantum-Guided Spectroscopy of Alcohol/Hydrocarbon Liquid Binary Solutions to Quantify Hydrogen Bonding, Poster presentation at the University of British Columbia, Reaction Mechanisms Conference, Vancouver, British Columbia, June 11, 2018
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Killian, W.G.; Bala, A.M.; Kakeshpour, T.; Peereboom, L.; Jackson, J.E.; Lira, C.T. Hydroxyl Infrared Spectroscopy in Liquid Mixtures Scaled with Quantum Calculations, Poster presentation at Michigan State University, CHEMS Research Forum, East Lansing, Michigan, May 10, 2018, 2nd Place Poster Award
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Bala, A.M.; Lira, C.T. Improving Solution Models by Understanding Hydrogen Bonding through Spectroscopy and Quantum Mechanics, Oral Presentation at Michigan State University, CHEMS Research Forum, East Lansing, Michigan, May 10, 2018.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Killian, W.G.; Bala, A.M.; Peereboom, L.; Jackson, J.E.; Lira, C.T. Simulation and Spectroscopy Guided Thermodynamic Modeling of Associating Systems, Poster presentation at Michigan State University, Engineering Research Symposium. East Lansing, Michigan, March 29, 2018
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Bala, A.M.; Cheluget, E.L.; Frank, T.C.; Jackson, J.E.; Killian, W.G.; Lira, C.T.; Mathias, P.M.; Patel, N.; Storer, J.A.; Vu, D.T. A Wertheim Activity Model for Associating Mixtures, Paper 574f, Presented at the Annual Meeting of AIChE, Oct 29-Nov 3, Minneapolis, MN, 2017.
• Type: Journal Articles Status: Under Review Year Published: 2018 Citation: Bala, A.M.; Lira, C.T. "Relation of Wertheim and Chemical Theories in Systems with Association and Solvation", in revision for Fluid Phase Equil.

Progress 10/01/16 to 09/30/17

Outputs
Target Audience:Academic professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?Peer-reviewed publications and meeting presentations. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? The Liao group is integrating solar, biological, and membrane technologies into wastewater treatment concept to create an energy-neutral small-scale wastewater treatment system that can significantly reduce mass of the wastewater, and simultaneously generate portable water. The Lira group is collaborating with major chemical producers (Dow, Honeywell, Fluor) to develop a new thermodynamic model to better represent hydrogen bonding systems that occur frequently when bioderived feedstocks are converted to chemical intermediates. The Lira group has found that while the hydrogen-bonding part of the thermodynamic model is important, the model for the nonhydrogen bonding portion is still important for representing the phase behavior. The Saffron group is collaborating with a small company to develop fuels and products from pyrolysis oil using electrocatalytic methods. Target products include cyclohexanol (a precursor to Nylon 6,6), ethylene glycol, propylene glycol and carbon foams. Alkylated cyclohexanols are also produced for use as liquid fuels. A detailed energy analysis has revealed that a system comprised of pyrolysis, electrocatalysis and hydroprocessing potentially produces nearly twice as much energy in liquid form versus classical cellulosic ethanol. The Miller group is engaged in development of efficient processes for converting biomass feedstocks to value-added fuels and chemicals.A major effort over the past year has been in the condensation chemistry of ethanol to higher alcohols, known as Guerbet reactions. We carry out the reaction in the condensed phase at substantially lower temperatures than the traditional vapor phase reactions, and have achieved higher alcohol selectivities as high as 80% of theoretical. The Dale group is involved in a number of bioenergy projects including distributed biomass processing systems, consolidated lignin conversion, high solid loading enzyme hydrolysis, and anaerobic digestion.Approximately ten distributed biorefineries based on corn stover could be established in the Midwest. Over 700 individual depot facilities participate in supplying the distributed biorefinery systems which collectively can produce greater than 12 hm3 of ethanol (3.3 billion gallons) per year. A systems biology approach was used to reveal the carbon utilization pattern and lignin degradation mechanisms in a unique lignin-utilizing Pseudomonas putida strain (A514). Lignin depolymerization and aromatic metabolism were optimized, while the β-oxidation of fatty acid was upregulated to produce polyhydroxyalkanoate (PHA) contents of 73% per cell dry weight (CDW). The Dale group investigated the effect of solids loading on simultaneous saccharification and co-fermentation (SSCF) of AFEXTM (ammonia fiber expansion) pretreated corn stover for ethanol production using a xylose fermenting strain Saccharomyces cerevisiae 424A(LNH-ST). Product inhibition was shown to be a significant factor, but can be overcome with product removal. Techno-economic analysis was employed to explore the economic possibilities of cellulosic ethanol production at high solids loadings. The results suggest that low-cost in situ removal of ethanol during SSCF would significantly improve the economics of high solids loading processes. Biogasdoneright™ demonstrates how it is possible to simultaneously increase the economic viability and stability of agriculture by reducing farm input costs and enabling farmers to produce food and fuel more sustainably.

Publications

• Type: Journal Articles Status: Published Year Published: 2016 Citation: Bala, A. M.; Lira, C. T. Relation of Wertheim Association Constants to Concentration-Based Equilibrium Constants for Mixtures with Chain-Forming Components. Fluid Ph. Equilib. 430, 47, (2016), doi: 10.1016/j.fluid.2016.09.015
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Lam, C.H.; Das, S.; Erickson, N. C.; Hyzer, C.D.; Garedew, M.; Anderson, J.E.; Wallington, T.J.; Tamor, M.A.; Jackson, J.E.; Saffron, C.M. Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading. Sustainable Energy and Fuels. 2017. 1. 258-266
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Lu Lin, Yanbing Cheng, Yunqiao Pu, Su Sun, Xiao Li, Mingjie Jin, Elizabeth A. Pierson, Dennis C. Gross, Bruce E. Dale, Susie Y. Dai, Arthur J. Ragauskas, Joshua S. Yuan. Systems biology-guided biodesign of consolidated lignin conversion. Green Chem., 18:55365547 (2016)
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Seungdo Kim, Bruce E. Dale. A distributed cellulosic biorefinery system in the US Midwest based on corn stover. Biofuels, Bioprod. Bioref. (2016)
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Mingjie Jin, Cory Sarks, Bryan D. Bals, Nick Posawatz, Christa Gunawan, Bruce E. Dale, Venkatesh Balan. Toward High Solids Loading Process for Lignocellulosic Biofuel Production at a Low Cost. Biotechnology and Bioengineering, 114(5):980-989 (2017)
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Bruce E. Dale, Fabrizio Sibilla, Claudio Fabbri, Marco Pezzaglia, Biagio Pecorino, Ezio Veggia, Angelo Baronchelli, Piero Gattoni, Parmiggiano Reggiano, Stefano Bozzetto. Biogasdoneright": An innovative new system is commercialized in Italy. Biofuels, Bioprod. Bioref. 10:341345 (2016)
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Jordison, T.; Miller, D.J. Impact of water on higher alcohol formation in condensed-phase Guerbet reactions of ethanol, Ind. Eng. Chem. Res. 55, 6579-6583 (2016)
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Nezam, I.; Peereboom, L.; Miller, D.J. Enhanced acrylate formation from pyrolysis of 2-acetoxypropionate esters, Organic Process Research & Development 21(5), 715-719 (2017)
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Saffron, C.M. A Hybrid Pyrolytic-Electrochemical Approach for Creating Fuels from Forest Biomass. Presentation given at the Michigan Forest Bioeconomy Conference. February 2nd, 2017. Grand Rapids, MI.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Garedew, M.; Hoang, A.; Sousa L.; Jackson, J.E.; Saffron, C.M. Pyrolytic and Electrochemical Upgrading of Lignins Extracted from Pretreated Biomass to Produce Liquid Fuel Intermediates and Value-Added Products. Presentation given at the American Institute for Chemical Engineering Annual Meeting. 2016. San Francisco, CA.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: 3. Saffron, C.M.; Carter, Z.; Das, S.; Fasahati, P.; Garedew, M.; Jackson, J.E.; Lin, Y.; Sak, R.; Wu, L. Technoeconomic Analysis of Pyrolysis and Electrocatalysis Depots. Presentation given at the American Institute for Chemical Engineering Annual Meeting. 2016. San Francisco, CA.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Saffron, C.M.; Garedew, M.; Sak, R.; Hao, P.; Jackson, J. Biomass Upgrading by Pyrolysis and Electrocatalysis Depots. Presentation given at the ASABE Annual International Meeting. 2016. Orlando, FL.
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Sak, R.; Saffron, C.M.; Juergens, A.; Brusstar, M.; Larson, B. Early Analysis of Electrocatalytic Hydrogenation of Unfractionated Bio-Oil Using Ruthenium as Catalyst. Poster given at the ASABE Annual International Meeting. 2016. Orlando, FL.

Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Academic Professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?The multistate meeting provides valuable interactions with other profressionals. A joint proposal was developed this year between Oregon State and Michigan State based on interactions initiated at the multistate meetings. What do you plan to do during the next reporting period to accomplish the goals?A representative from MSU will attend the annual meeting to continue to represent MSU.

Impacts
What was accomplished under these goals? Biological conversion technologies Task: Develop pretreatment methods for biological conversion processes. The David Hodge lab has fractionated lignins derived from biorefining processes to yield lignins enriched in targeted properties that were subjected to catalytic oxidation. It was demonstrated the aromatic monomer yields could be correlated to lignin properties. Ongoing work is focused on understanding cell wall properties that impact alkaline and oxidative pretreatment outcomes. We recently identified that that cell wall-associated transition metals provide a significant positive contribution to delignification efficacy during oxidative pretreatments and that these are strongly correlated to improvements in enzymatic hydrolysis yields. Task. Conversion Processes The Mark Worden lab is developing technology for fermentations of gas feedstocks such as methane and hydrogen. These fermentations present a new set of engineering challenges: (1) low aqueous solubility of gases (2) high molar gas requirement (3) possible formation of explosive gas mixtures. Microbubbles are proposed as a part of the solution to these challenges. Microbubbles have an extremely large surface area per unit gas volume and a mass-transfer driving force that increases as the bubble shrinks. They offer the potential for extremely high volumetric mass-transfer coefficients (kLa) and gas-conversion efficiencies without forming incompatible gas mixtures. Experimental and modeling work is ongoing to measure and model the mass transfer coefficients. The model simulates the lower, highly turbulent region of the column as one large CSTR and the upper, less turbulent region as a series of smaller CSTRs. The Dennis Miller group focuses on developing new pathways for biofuel components and commodity chemicals. The study of the chemistry of ethanol condensation to butanol and higher alcohols, useful as biofuel constituents, have been recently examined. Reactions are carried out in a continuous flow reactor system that gives selectivity to desired alcohols that is equal to or higher than that obtained in stirred batch reactors. Catalyst composition is being optimized to achieve the highest activity and selectivity to desired products. A detailed thermodynamic model of the phase equilibrium in the ethanol condensation reaction system that allows more accurate determination of the products formed in reaction has also been developed. In a second project, the formation of furan dicarboxylic acid (FDCA) from uronic acids, found in fruit pectin and in alginates, has been studied using ionic liquids as the reaction media. Good yields of FDCA have been achieved, and recovery of the FDCA is readily accomplished by crystallization. The Carl Lira group focuses on property modeling of a biorenewable chemicals and fuels. Industry is finding many challenges in modeling conversion of polar feedstocks to hydrocarbons. Models of hydrogen-bonding fluids are under development. We have demonstrated that the chemical theory and Wertheim's theory are exactly equivalent numerically, though the equations and theoretical development are quite different. Spectroscopic measurements and molecular simulations will be used to further characterize the hydrogen bonding parameters that are currently fitted macroscopically. We are coding a model that can be used throughout industry in process simulators. Objective: Thermochemical Conversion Task. Conversion The Chris Saffron group envisions that use of torrefied biomass can prevent the unnecessary decommissioning of solid fuel furnaces that is occurring in response to recent EPA regulations. MSU's T.B. Simon Power Plant has performed a test burn of approximately 300 tons of torrefied wood pellets to determine the efficacy of this technology. Though largely successful, pellets are costly and certain fuel properties, e.g. grindability and hydrophobicity, could be improved. To examine different feedstocks and processing conditions, briquettes of torrefied biomass have been exposed outdoors to several freeze-thaw cycles to examine integrity. Water immersion, contact angle and droplet penetration methods are being developed to assess hydrophobicity. The different bonding configurations amongst the monolignols of lignin are believed to be especially important for making stable pellets or briquettes. Task. Catalytic upgrading of thermochemical products The Saffron and Jackson labs performs pyrolysis to create liquid bio-oil and electrocatalysis to reductively stabilize the bio-oil. Pyrolysis and electrocatalysis are envisioned at decentralized depots that are located near the areas of biomass harvest, with the goal of creating an energy dense fuel intermediate. Stable bio-oil is then hydroprocessed in a large central facility to create hydrocarbon fuels. As part of a related project, the lignin-derived fraction of bio-oil, comprised of molecules like guaiacol and syringol are demethoxylated and saturated to form cyclohexanol, a valuable Nylon 6,6 precursor. A systemwide energy audit reveals substantial energy upgrading of biomass when bio-oil is stabilized electrocatalytically. Such an approach is especially "green" when wind turbines and solar photovoltaics provide the electrical power. Objective: Supply Task. Supply systems Bruce Dale group has studied the impact of farmgate pricing on biofuel feedstocks. Most economic models consider low farmgate prices, which will have a negative impact on farmer participation. The revised premise is that the final ethanol market price will dictate market penetration. At $40/dry ton 4.5 billion gallons of ethanol are projected from 43 biorefineries, and impacting constituencies for approximately 20% of the US senators and representatives. Doubling the farmgate price to $80/dry ton is projected to increase ethanol production by almost a factor of 10 to 42.1 billion gallons of ethanol from 207 biorefineries, impacting constituencies for approximately 75% of the US senators and representatives. The weighted selling price at $40/dry ton is $2.18/gal, and when double to $80/dry ton the selling price is $2.46/gal. For feedstock prices below $60/ton, each $1/dry ton increase in feedstock prices will generate 5700 FTEs. Above $65/ton, each $1/dry ton increase will generate about 1400 FTEs. Jobs are considered in all aspects of production from growing, plant construction and operations, and fuel marketing and distribution. The US Renewable Fuels Standard (RFS) requires that about 16 billlion gallons per year of cellulosic biofuels be produced with a greenhouse gas (GHG) profile that is 60% less than petroleum-derived fuels. We have continued our modeling of cellulosic biomass logistics and supply systems to including better understanding of distributed biorefineries based on corn stover. Because of the relatively low geographic density of stover and the consequent high greenhouse gas emissions due to stover transport to the biorefineries, we find that it will be impossible to simultaneously meet both the volume and GJG requirements of the RFS using corn stover only. Only about 4 billion gallons per year of cellulosic biofuels based on stover can be produced with the desired GHG emissions.

Publications

Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Academic Professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?Results were communicated to the project team at the annual meeting. Personal interactions were helpful in communicating the new knowledge. The interdisciplinary nature of the committee is beneficial. What do you plan to do during the next reporting period to accomplish the goals?A representative from MSU will attend the annual meeting to continue to represent MSU.

Impacts
What was accomplished under these goals? Biological conversion technologies Task: Develop pretreatment methods for biological conversion processes. The David Hodge lab has fractionated lignins derived from biorefining processes to yield lignins enriched in targeted properties that were subjected to catalytic oxidation. It was demonstrated the aromatic monomer yields could be correlated to lignin properties. Ongoing work is focused on understanding cell wall properties that impact alkaline and oxidative pretreatment outcomes. We recently identified that that cell wall-associated transition metals provide a significant positive contribution to delignification efficacy during oxidative pretreatments and that these are strongly correlated to improvements in enzymatic hydrolysis yields. Task. Conversion Processes The Mark Worden lab is developing technology for fermentations of gas feedstocks such as methane and hydrogen. These fermentations present a new set of engineering challenges: (1) low aqueous solubility of gases (2) high molar gas requirement (3) possible formation of explosive gas mixtures. Microbubbles are proposed as a part of the solution to these challenges. Microbubbles have an extremely large surface area per unit gas volume and a mass-transfer driving force that increases as the bubble shrinks. They offer the potential for extremely high volumetric mass-transfer coefficients (kLa) and gas-conversion efficiencies without forming incompatible gas mixtures. Experimental and modeling work is ongoing to measure and model the mass transfer coefficients. The model simulates the lower, highly turbulent region of the column as one large CSTR and the upper, less turbulent region as a series of smaller CSTRs. The Dennis Miller group focuses on biofuel components and commodity chemicals. The formation of propylene oxide (PO), a valuable intermediate for plastics production, from propylene glycol was achieved with over 85% selectivity in a continuous flow reactor. In a second project, details of the chemistry of ethanol condensation to butanol and higher alcohols, useful as biofuel constituents, have been recently examined. Adding or removing molecular hydrogen (H2) from the reaction mixture changes the direction of reactions substantially and gives insights into the key reactions. A detailed thermodynamic model of the phase equilibrium in the ethanol condensation reaction system that allows more accurate determination of the products formed in reaction has also been developed. Finally, the mechanism of catalyst deactivation in methyl furfural hydrogenation to dimethyl furan has been investigated; this reaction is representative of several furan-based reaction systems, all of which have exhibited loss of catalyst activity with time on stream. The Carl Lira group focuses on property modeling of a biorenewable chemicals and fuels. Surrogate models of biorenewable-sourced jet fuel have been improved to match the cloud points within 6% and the distillation curves within an average of 5K. Bulk moduli of six alternative fuels and their blends with JP-8 have been measured up to 16,000 psi at 35C and 65C. The SAFT-BACK equation was found to be incapable or representing bulk modulus of aviation fuels. The GC-PC-SAFT equation is systematically low by about 15%. Property modeling is also important for process design of conversion processes. Industry is finding many challenges in modeling conversion of polar feedstocks to hydrocarbons. Models of hydrogen-bonding fluids are under development. We have demonstrated that the chemical theory and Wertheim's theory are exactly equivalent numerically, though the equations and theoretical development are quite different. Spectroscopic measurements and molecular simulations will be used to further characterize the hydrogen bonding parameters that are currently fitted macroscopically. Objective: Thermochemical Conversion Task. Conversion The Chris Saffron group envisions that use of torrefied biomass can prevent the unnecessary decommissioning of solid fuel furnaces that is occurring in response to recent EPA regulations. MSU's T.B. Simon Power Plant has performed a test burn of approximately 300 tons of torrefied wood pellets to determine the efficacy of this technology. Though largely successful, pellets are costly and certain fuel properties, e.g. grindability and hydrophobicity, could be improved. To examine different feedstocks and processing conditions, briquettes of torrefied biomass have been exposed outdoors to several freeze-thaw cycles to examine integrity. Water immersion, contact angle and droplet penetration methods are being developed to assess hydrophobicity. The different bonding configurations amongst the monolignols of lignin are believed to be especially important for making stable pellets or briquettes. Task. Catalytic upgrading of thermochemical products The Saffron and Jackson labs performs pyrolysis to create liquid bio-oil and electrocatalysis to reductively stabilize the bio-oil. Pyrolysis and electrocatalysis are envisioned at decentralized depots that are located near the areas of biomass harvest, with the goal of creating an energy dense fuel intermediate. Stable bio-oil is then hydroprocessed in a large central facility to create hydrocarbon fuels. As part of a related project, the lignin-derived fraction of bio-oil, comprised of molecules like guaiacol and syringol are demethoxylated and saturated to form cyclohexanol, a valuable Nylon 6,6 precursor. A system-wide energy audit reveals substantial energy upgrading of biomass when bio-oil is stabilized electrocatalytically. Such an approach is especially "green" when wind turbines and solar photovoltaics provide the electrical power. Objective: Supply Task. Supply systems Bruce Dale group has studied the impact of farmgate pricing on biofuel feedstocks. Most economic models consider low farmgate prices, which will have a negative impact on farmer participation. The revised premise is that the final ethanol market price will dictate market penetration. At $40/dry ton 4.5 billion gallons of ethanol are projected from 43 biorefineries, and impacting constituencies for approximately 20% of the US senators and representatives. Doubling the farmgate price to $80/dry ton is projected to increase ethanol production by almost a factor of 10 to 42.1 billion gallons of ethanol from 207 biorefineries, impacting constituencies for approximately 75% of the US senators and representatives. The weighted selling price at $40/dry ton is $2.18/gal, and when double to $80/dry ton the selling price is $2.46/gal. For feedstock prices below $60/ton, each $1/dry ton increase in feedstock prices will generate 5700 FTEs. Above $65/ton, each $1/dry ton increase will generate about 1400 FTEs. Jobs are considered in all aspects of production from growing, plant construction and operations, and fuel marketing and distribution.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Lira, C.T. "State of Michigan Station Report to S1041 Committee", presented at the S1041 annual meeting, Wooster, OH, Aug 10-11, 2015.

Progress 01/28/14 to 09/30/14

Outputs
Target Audience: Academic Professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? Results were communicated to the project team at the meeting. Personal interactions were helpful in communicating the new knowledge. The interdisciplinary nature of the committee is beneficial. What do you plan to do during the next reporting period to accomplish the goals? A representative from MSU will attend the annual meeting to continue to represent MSU.

Impacts
What was accomplished under these goals? MSU has developed surrogate models to represent blends of second generation alternative jet fuels with petroleum fuels. Both Fischer-Tropsch and reformed hydrotreated oils are considered. Modeled properties include distillation curve, cloud point, cetane number. AFEX pretreatment of cellulosic feedstocks can be profitably practiced in small (100-200 ton per day) depots (i.e., distributed processing facilities). Following AFEX pretreatment, biomass can be cheaply pelleted to produce a dense, stable material that flows and handles like corn grain. AFEX pretreated biomass can be used either as ruminant feed or biofuel feedstock: ruminant feedstock value was established this year in large scale feeding trials. Use as ruminant feed allows biofuel industry to build on an established market/feedstock, just like the successful corn ethanol industry. MSU has obtained conversion of propylene glycol to propylene oxide in selectivities > 75% using potassium catalysts. MSU has demonstrated ethanol condensation of ethanol to higher alcohols, predominately butanol. MSU has developed a new catalytic route for sugar dehydration to furan dicarboxylic acid, an emerging monomer for low permeability plastics. MSU is collaborating with E2Tec on reactive distillation of citric acid.

Publications

• Type: Conference Papers and Presentations Status: Accepted Year Published: 2014 Citation: Lira, C.T. Michigan Station Report, presented at the S1041 Annual Meeting, New Orleans, LA, August 4-6, 2014.